CN105111729B - Environmental protection flame retardant carbon fiber reinforced polyamide composite material and its preparation method and application - Google Patents

Environmental protection flame retardant carbon fiber reinforced polyamide composite material and its preparation method and application Download PDF

Info

Publication number
CN105111729B
CN105111729B CN201510571583.8A CN201510571583A CN105111729B CN 105111729 B CN105111729 B CN 105111729B CN 201510571583 A CN201510571583 A CN 201510571583A CN 105111729 B CN105111729 B CN 105111729B
Authority
CN
China
Prior art keywords
carbon fiber
flame retardant
environmental protection
composite
fiber reinforced
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201510571583.8A
Other languages
Chinese (zh)
Other versions
CN105111729A (en
Inventor
郝建鑫
邓爵安
郝源增
陈瑜
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GUANGZHOU SUPER-DRAGON ENGINEERING PLASTICS Co Ltd
Original Assignee
GUANGZHOU SUPER-DRAGON ENGINEERING PLASTICS Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by GUANGZHOU SUPER-DRAGON ENGINEERING PLASTICS Co Ltd filed Critical GUANGZHOU SUPER-DRAGON ENGINEERING PLASTICS Co Ltd
Priority to CN201510571583.8A priority Critical patent/CN105111729B/en
Publication of CN105111729A publication Critical patent/CN105111729A/en
Application granted granted Critical
Publication of CN105111729B publication Critical patent/CN105111729B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/9258Velocity
    • B29C2948/9259Angular velocity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92704Temperature
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/22Halogen free composition

Abstract

The invention belongs to modified polymer material field, discloses a kind of environmental protection flame retardant carbon fiber reinforced polyamide composite material and its preparation method and application.The composite material includes the component of following mass fraction:Polyamide 7.7~70.7%;Carbon fiber 15~55%;Kynoar 10~25%;Composite flame-retardant agent 4~15%;Dispersant 0.2~1%;Other auxiliary agents 0.1~0.3%.The Kynoar of high molecular weight and the excellent compatibility of polyamide material can form big network structure in polymeric substrate, make composite material that there is certain flame retardant property, the nitrogen phosphorus flame retardant of appropriate amount is added, which can reach higher environmental protection flame retardant grade.The present invention greatly reduces the dosage of fire retardant, carbon fiber reinforced polyamide material is reduced density of material while best mechanical property is reached, improve the fire resistance of material by adding Kynoar.

Description

Environmental protection flame retardant carbon fiber reinforced polyamide composite material and its preparation method and application
Technical field
The invention belongs to modified polymer material field, more particularly to a kind of environmental protection flame retardant carbon fiber reinforced polyamide is compound Material and its preparation method and application.
Background technology
Polyamide be on molecular backbone containing recurring amide radical group-[NHCO]-thermoplastic resin general name.This kind of polymer With many excellent performances such as wear-resisting, oil resistant, self-lubricating, impact resistance, and it is widely used in mechanical equipment, automobile making, instrument The fields such as instruments and meters.Highly polar amide group and long flexible aliphatic segment in fatty polyamide molecular structure make this kind of Material has limited oxygen index low, meets the shortcomings of fire easily burns.The especially polyamide of some glasses or fibre reinforced For material when doing thin-gage goods, due to glass fibre or the wick effect of carbon fiber, it is fire-retardant that this kind of material is difficult to realize material With the balance of toughness.Therefore, the temperature in use and environmental protection flame retardant performance of polyamide material how are improved, is that polyamide material is modified The important research topic in one, field.
Carbon fiber is a kind of new fiber materials of phosphorus content more than 95%, it is with organic fiber, such as acrylics filament (PAN), pitch and viscose rayon etc. do raw material, the micro crystal graphite fiber obtained in inert gas after high-temperature calcination graphite Material.Since carbon fiber has in physical property, proportion is small, intensity is big, modulus is high, linear expansion coefficient is small, electric conductivity is strong, leads The features such as heating rate is high, this kind of material are had been widely used in the enhancing and functional modification of thermoplasticity and thermosetting resin.Profit Its physical and mechanical property of the thermoplastic being modified with carbon fiber and heat resistance have great raising, such as polyamide 66 material The tensile strength of material improves nearly 3 times after the carbon fiber of material addition 20%, and bending modulus improves nearly 4 times, and heat distortion temperature carries Up to 250 DEG C.By the optimization to surface treatment of carbon fibers mode and complex machining process, carbon fiber modifying polyamide material is improved The performance of material, will be an important research direction of following reinforced polyamide development.
The characteristics of higher and higher, the present invention are required to the lightening and high performance of material for Current electronic electric field A kind of environmental protection flame retardant carbon fiber reinforced polyamide composite material is developed, which is suitable for preparing by injection molding light Quantify more demanding thin-gage goods, applied to requiring environmental protection flame retardant, antistatic and more demanding to material mechanical performance electricity Sub- device and electric tool.
The content of the invention
In order to overcome the shortcomings and deficiencies of the prior art described above, primary and foremost purpose of the invention is to provide a kind of environmental protection flame retardant Carbon fiber reinforced polyamide composite material.The composite material of the present invention has high intensity, high fire-retardance grade, low-density, low warpage The features such as rate.
Another object of the present invention is to provide a kind of preparation of above-mentioned environmental protection flame retardant carbon fiber reinforced polyamide composite material Method.
Still a further object of the present invention be to provide above-mentioned environmental protection flame retardant carbon fiber reinforced polyamide composite material electronic apparatus, The application in the fields such as high iron, electric tool.Thin-gage goods prepared by the composite material of the present invention has intensity height, anti-flammability Can be good, warpage is low the features such as, need to use thin-walled material particularly suitable for preparing laptop, phone housing, capacitor etc. The field of material.
The purpose of the present invention is realized by following proposal:
A kind of carbon fiber reinforced polyamide composite material of environmental protection flame retardant, includes the component of following mass fraction:
The mass fraction of above-mentioned polyamide is preferably 40~50%.
Above-mentioned polyamide can be at least one of polyamide 6 (PA6) and polyamide 66 (PA66), be preferably polyamide 6。
It is furthermore preferred that the low-viscosity polyamides 6 that it is 2.0~2.8Pas that above-mentioned polyamide, which is viscosity,.
The mass fraction of above-mentioned carbon fiber is preferably 30~40%.
Above-mentioned carbon fiber can be in the carbon fiber of polyacrylonitrile base material, viscose carbon fiber and pitch silk carbon fiber extremely Few one kind.
Preferably, above-mentioned carbon fiber is the carbon fiber of polyacrylonitrile base material.
It is furthermore preferred that above-mentioned carbon fiber is 4~8 μm of filament diameter, the polyacrylonitrile of 200~800tex of synnema line density The carbon fiber of base material.The carbon fiber strength is high, can effectively improve the shock resistance of polyamide.
The mass fraction of above-mentioned Kynoar is preferably 12~20%.
Above-mentioned Kynoar (PVDF) is preferably the high molecular weight PVDF that molecular weight is more than or equal to 1,000,000, is such as included: 5301,9009 etc. of U.S. Su Wei, wherein more preferably 5301., can since Kynoar has higher limited oxygen index To improve the flame retardancy of composite material;In addition the Kynoar of high molecular weight can form net structure in the composite, It can prevent material from producing drip phenomenon in combustion.In addition, high molecular weight Kynoar can also be used as toughener effective Improve the shock resistance of material.
Above-mentioned composite flame-retardant agent is formed by halogen-free flame retardants and synergistic flame retardant compounding.
Above-mentioned halogen-free flame retardants is the expansion type flame retardant of triazines.
Preferably, above-mentioned halogen-free flame retardants can be cyanurate, cyanurate derivative, melamine polyphosphate, guanidinesalt At least one of with dicyandiamide salt.
It is furthermore preferred that above-mentioned halogen-free flame retardants is melamine polyphosphate.
Above-mentioned fire retarding synergist is the inorganic salts compound of reaction of decomposing that can be heated in alkaline conditions.
Preferably, above-mentioned fire retarding synergist is iron chloride (FeCl3), zinc borate (2ZnO3B2O3·3.5H2O), oxygen Change magnesium (MgO) and aluminium oxide (Al2O3At least one of).
It is furthermore preferred that above-mentioned fire retarding synergist is FeCl3
The mass ratio of halogen-free flame retardants and synergistic flame retardant is 5 in above-mentioned composite flame-retardant agent:1~2:1, it is preferably 3:1.
The mass fraction of above-mentioned dispersant is preferably 0.5~0.8%.
Above-mentioned dispersant can be pentaerythritol esters dispersant, silicone dispersant and dendrimer at least It is a kind of.
Preferably, above-mentioned dispersant is pentaerythritol oleate, pentaerythritol stearate (PETS), the double hard esters of ethylene At least one of acid amides (EBS) and organic silicon dispersant (such as E525, Evonik).
It is furthermore preferred that above-mentioned dispersant is organic silicon dispersant (such as E525, Evonik).
The mass fraction of above-mentioned other auxiliary agents is preferably 0.2%.
Above-mentioned other auxiliary agents can be this area it is common suitable at least one of processing aid of polyamide system, Such as processing stabilizers, antioxidant.
Preferably, above-mentioned antioxidant for phosphite ester kind antioxidant (such as 3,9- bis- (2,4- dicumyl phenoxy group) -2,4, 8,10- tetra- oxa- -3,9- bis- phospha spiral shell [5.5] hendecane (S9228), three (2,4- di-tert-butyl-phenyl) phosphite esters (168))。
It is furthermore preferred that above-mentioned antioxidant is three (2,4- di-tert-butyl-phenyl) phosphite esters (irgasfos 168).
Present invention also offers a kind of preparation method of above-mentioned environmental protection flame retardant carbon fiber reinforced polyamide composite material, including Operating procedure in detail below:
(1) polyamide, Kynoar, composite flame-retardant agent, dispersant and other auxiliary agents are added in homogenizer and mixed Close uniform;
(2) mixed material in step (1) is added in double screw extruder by main spout, carbon fiber is through twin-screw Extruder vent is added in double screw extruder, and melt blending, extruding pelletization, that is, obtain environmental protection flame retardant fibre reinforced polyamides Amine composite material.
It is room temperature~80 DEG C that the optimum condition of mixing described in step (1), which refers to mixing temperature, 200~400r/min's 10~30min is stirred under speed.
The screw speed of the host of double screw extruder described in step (2) is 350~430r/min, hopper feed spiral shell The rotating speed of bar is 24~35r/min.
The temperature of melt blending described in step (2) is preferably that the temperature of each bringing-up section of extruder is 180~255 DEG C.
Extruding pelletization described in step (2) is preferably through extruding pelletization again after water-bath cooling system.
The physical and mechanical property for the environmental protection flame retardant carbon fiber reinforced polyamide composite material that the present invention is prepared, processability Energy, appearance are functional, and relatively common carbon fiber reinforced polyamide material has the resistance to warping of higher, can be applied to electricity In the fields such as sub- electric appliance, high iron, electric tool.Be particularly suitable for application prepare some will to the strength of materials and lightweight Seek high thin-gage goods.
Kynoar is a kind of flexible polymer of high Oil repellent, and compared to polytetrafluoroethylene (PTFE), its crystallinity is lower, with The compatibility of polyamide material is more preferable.The present invention is compound using Kynoar and polyamide, as polymerization after molten alloy Thing base material, makes composite material have certain flame retardant property, and the material can reach after the nitrogen phosphorus flame retardant of appropriate amount is added To higher environmental protection flame retardant grade.Kynoar with it is polyamide blended after can accelerate the crystallization rate of polyamide substrate, make Obtained carbon fiber reinforced polyamide material has excellent physical and mechanical property, and has lower molding shrinkage and warpage Rate.
The fire retardant mechanism of composite material of the present invention is:The good phase of the Kynoar of high molecular weight and polyamide material Capacitive can form big network structure in polymeric substrate, on the one hand which can improve the limit of base material Oxygen index (OI), on the other hand can play the role of anti-dripping melt during material combustion;Nitrogen phosphorus flame retardant can be fired in base material The high-temperature material surface of burning forms the carbon-coating of densification, and discharges non-flammable gases and form protective layer to base material;Carbon fiber conduct Reinforcing material can both provide the mechanical property of higher for composite material, and high carbon skeleton can be also used as in the combustion process of material More preferable protection is formed in the burning surface of material;On the one hand synergistic flame retardant used in the present invention can be used as catalyst to promote Reacted into nitrogen phosphorus flame retardant into carbon, still further aspect can occur under the high temperature and alkaline condition that polyamide substrate is burnt Decomposition reaction, absorbs the heat produced in combustion process.
The present invention is had the following advantages and beneficial effect relative to the prior art:
(1) environmental protection flame retardant carbon fiber reinforced polyamide composite material of the invention has good mechanical property, relatively low Molding shrinkage and warpage, are very helpful for the warpage properties tool for reducing material.
(2) present invention greatly reduces the dosage of fire retardant, makes fibre reinforced polyamides by adding Kynoar Amine material reduces density of material while best mechanical property is reached, and improves the fire resistance of material.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Agents useful for same is commercially available in the following example.
Double screw extruder used is that draw ratio L/D is 40 in the following example:1, screw diameter is the parallel of 30mm Double screw extruder, the screw speed of host is 350r/min, and the rotating speed of hopper feed screw rod is 28r/min, sets extruder Each section of temperature from hopper to die head is respectively (totally nine area):180 DEG C, 225 DEG C, 230 DEG C, 240 DEG C, 245 DEG C, 255 DEG C, 250 DEG C, 245 DEG C, 245 DEG C.
Embodiment 1
By the PA6 (M2400, Yueyang petrochemical industry) of 826g, the PVDF (5301, SOLEF) of 240g, the composite flame-retardant agent of 220g (melamine polyphosphate and FeCl3Mass ratio be 3:1), the organosilicone spreading agent (E525, Evonik) of 10g, the Asia of 4g Phosphonic acid ester irgasfos 168 is added in high speed blender, after stirring 10min at a temperature of 50 DEG C with the speed of 150r/min, Said mixture material is added in double screw extruder by main spout, at the same by the carbon fiber of 700g (T700SC-12K, Toray) it is added to by exhaust outlet in double screw extruder, environmental protection flame retardant carbon fiber is obtained after melt blending, water cooling pelletizing, drying Reinforced polyamide composite material.
Embodiment 2
By the PA6 (M2400, Yueyang petrochemical industry) of 666g, the PVDF (5301, SOLEF) of 400g, the composite flame-retardant agent of 220g (melamine polyphosphate and FeCl3Mass ratio be 3:1), the organosilicone spreading agent (E525, Evonik) of 10g, the Asia of 4g Phosphonic acid ester irgasfos 168 is added in high speed blender, after stirring 10min at a temperature of 50 DEG C with the speed of 150r/min, Said mixture material is added in double screw extruder by main spout, at the same by the carbon fiber of 700g (T700SC-12K, Toray) it is added to by exhaust outlet in double screw extruder, environmental protection flame retardant carbon fiber is obtained after melt blending, water cooling pelletizing, drying Reinforced polyamide composite material.
Embodiment 3
By the PA6 (M2400, Yueyang petrochemical industry) of 766g, the PVDF (5301, SOLEF) of 300g, the composite flame-retardant agent of 220g (melamine polyphosphate and FeCl3Mass ratio be 3:1), the organosilicone spreading agent (E525, Evonik) of 10g, the Asia of 4g Phosphonic acid ester irgasfos 168 is added in high speed blender, after stirring 10min at a temperature of 50 DEG C with the speed of 150r/min, Said mixture material is added in double screw extruder by main spout, at the same by the carbon fiber of 700g (T700SC-12K, Toray) it is added to by exhaust outlet in double screw extruder, environmental protection flame retardant carbon fiber is obtained after melt blending, water cooling pelletizing, drying Reinforced polyamide composite material.
Embodiment 4
By the PA6 (M2400, Yueyang petrochemical industry) of 1106g, the PVDF (5301, SOLEF) of 300g, the composite flame-retardant agent of 80g (melamine polyphosphate and FeCl3Mass ratio be 3:1), the organosilicone spreading agent (E525, Evonik) of 10g, the Asia of 4g Phosphonic acid ester irgasfos 168 is added in high speed blender, after stirring 10min at a temperature of 50 DEG C with the speed of 150r/min, Said mixture material is added in double screw extruder by main spout, at the same by the carbon fiber of 700g (T700SC-12K, Toray) it is added to by exhaust outlet in double screw extruder, environmental protection flame retardant carbon fiber is obtained after melt blending, water cooling pelletizing, drying Reinforced polyamide composite material.
Embodiment 5
By the PA6 (M2400, Yueyang petrochemical industry) of 760g, the PVDF (5301, SOLEF) of 300g, the composite flame-retardant agent of 220g (melamine polyphosphate and FeCl3Mass ratio be 3:1), the organosilicone spreading agent (E525, Evonik) of 16g, the Asia of 4g Phosphonic acid ester irgasfos 168 is added in high speed blender, after stirring 10min at a temperature of 50 DEG C with the speed of 150r/min, Said mixture material is added in double screw extruder by main spout, at the same by the carbon fiber of 700g (T700SC-12K, Toray) it is added to by exhaust outlet in double screw extruder, environmental protection flame retardant carbon fiber is obtained after melt blending, water cooling pelletizing, drying Reinforced polyamide composite material.
Embodiment 6
By the PA6 (M2400, Yueyang petrochemical industry) of 866g, the PVDF (5301, SOLEF) of 300g, the composite flame-retardant agent of 220g (melamine polyphosphate and FeCl3Mass ratio be 3:1), the organosilicone spreading agent (E525, Evonik) of 10g, the Asia of 4g Phosphonic acid ester irgasfos 168 is added in high speed blender, after stirring 10min at a temperature of 50 DEG C with the speed of 150r/min, Said mixture material is added in double screw extruder by main spout, at the same by the carbon fiber of 600g (T700SC-12K, Toray) it is added to together in double screw extruder by exhaust outlet, environmental protection flame retardant carbon is obtained after melt blending, water cooling pelletizing, drying Fibre-reinforced polyamide composite material.
Embodiment 7
By the PA6 (M2400, Yueyang petrochemical industry) of 666g, the PVDF (5301, SOLEF) of 300g, the composite flame-retardant agent of 220g (melamine polyphosphate and FeCl3Mass ratio be 3:1), the organosilicone spreading agent (E525, Evonik) of 10g, the Asia of 4g Phosphonic acid ester irgasfos 168 is added in high speed blender, after stirring 10min at a temperature of 50 DEG C with the speed of 150r/min, Said mixture material is added in double screw extruder by main spout, at the same by the carbon fiber of 800g (T700SC-12K, Toray) it is added to by exhaust outlet in double screw extruder, environmental protection flame retardant carbon fiber is obtained after melt blending, water cooling pelletizing, drying Reinforced polyamide composite material.
Embodiment 8
By the PA6 (M2400, Yueyang petrochemical industry) of 366g, the PVDF (5301, SOLEF) of 300g, the composite flame-retardant agent of 220g (melamine polyphosphate and FeCl3Mass ratio be 3:1), the organosilicone spreading agent (E525, Evonik) of 10g, the Asia of 4g Phosphonic acid ester irgasfos 168 is added in high speed blender, after stirring 10min at a temperature of 50 DEG C with the speed of 150r/min, Said mixture material is added in double screw extruder by main spout, at the same by the carbon fiber of 1100g (T700SC-12K, Toray) it is added to by exhaust outlet in double screw extruder, environmental protection flame retardant carbon fiber is obtained after melt blending, water cooling pelletizing, drying Reinforced polyamide composite material.
Embodiment 9
By the PA6 (M2400, Yueyang petrochemical industry) of 800g, the PVDF (5301, SOLEF) of 300g, the composite flame-retardant agent of 220g (melamine polyphosphate and FeCl3Mass ratio be 3:1), the organosilicone spreading agent (E525, Evonik) of 10g, the Asia of 4g Phosphonic acid ester irgasfos 168 is added in high speed blender, after stirring 10min at a temperature of 50 DEG C with the speed of 150r/min, Said mixture material is added in double screw extruder by main spout, at the same by the carbon fiber of 666g (T700SC-12K, Toray) it is added to by exhaust outlet in double screw extruder, environmental protection flame retardant carbon fiber is obtained after melt blending, water cooling pelletizing, drying Reinforced polyamide composite material.
Embodiment 10
By the PA6 (M2400, Yueyang petrochemical industry) of 1000g, the PVDF (5301, SOLEF) of 300g, the composite flame-retardant agent of 220g (melamine polyphosphate and FeCl3Mass ratio be 3:1), the organosilicone spreading agent (E525, Evonik) of 10g, the Asia of 4g Phosphonic acid ester irgasfos 168 is added in high speed blender, after stirring 10min at a temperature of 50 DEG C with the speed of 150r/min, Said mixture material is added in double screw extruder by main spout, at the same by the carbon fiber of 466g (T700SC-12K, Toray) it is added to by exhaust outlet in double screw extruder, environmental protection flame retardant carbon fiber is obtained after melt blending, water cooling pelletizing, drying Reinforced polyamide composite material.
Comparative example 1
By the PA6 (M2400, Yueyang petrochemical industry) of 1066g, composite flame-retardant agent (melamine phosphate and the FeCl of 220g3's Mass ratio is 3:1), the organosilicone spreading agent (E525, Evonik) of 10g, the phosphiinic acid ester irgasfos 168 of 4g are added at a high speed In blender, after stirring 10min at a temperature of 50 DEG C with the speed of 150r/min, said mixture material is added by main spout Enter in double screw extruder, while the carbon fiber (T700SC-12K, Toray) of 700g is added to twin-screw by exhaust outlet and is squeezed Go out in machine, carbon fiber reinforced polyamide composite material is obtained after melt blending, water cooling pelletizing, drying.
Comparative example 2
By the PA6 (M2400, Yueyang petrochemical industry) of 886g, composite flame-retardant agent (melamine polyphosphate and the FeCl of 400g3 Mass ratio be 3:1), the organosilicone spreading agent (E525, Evonik) of 10g, the phosphiinic acid ester irgasfos 168 of 4g are added to height In fast blender, after stirring 10min at a temperature of 50 DEG C with the speed of 150r/min, said mixture material is passed through into main spout Add in double screw extruder, while the carbon fiber (T700SC-12K, Toray) of 700g is added to twin-screw by exhaust outlet In extruder, carbon fiber reinforced polyamide composite material is obtained after melt blending, water cooling pelletizing, drying.
The carbon fiber reinforced polyamide material that embodiment 1~10 and comparative example 1~2 are prepared is according to GB, ISO Mechanical property and fire resistance test are carried out with standards such as UL94, the results are shown in Table 1.
The performance test of 1 carbon fiber reinforced polyamide composite material of table
By embodiment 1~10 as it can be seen that the environmental protection flame retardant carbon fiber reinforced polyamide material of the present invention has excellent physics Mechanical property and good processing performance.Since Kynoar has higher limited oxygen index, using Kynoar with The carbon fibre reinforced composite obtained after polyamide is compound can largely reduce the dosage of fire retardant, and flame retarding efficiency can reach To the flame retardant rating of UL94-1.6mm V0, and the material flame retardant effect for not adding Kynoar is poor, even if substantial increase resistance The dosage flame retardant effect of combustion agent is only capable of the level (comparative example 2) for reaching UL94-1.6mm V1, and burning time is compared with embodiment It is long.Result of the test again shows that, when not having to add Kynoar in system, the impact strength of material and elongation at break be all Having largely reduces, this explanation Kynoar can play good toughening effect in the composite.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention and from above-described embodiment Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims (8)

1. a kind of environmental protection flame retardant carbon fiber reinforced polyamide composite material, it is characterised in that by the component group of following mass fraction Into:
The Kynoar is more than or equal to 1,000,000 high molecular weight Kynoar for molecular weight;
The carbon fiber is at least one in the carbon fiber, viscose carbon fiber and pitch silk carbon fiber of polyacrylonitrile base material Kind;
The composite flame-retardant agent is made of halogen-free flame retardants and synergistic flame retardant;
The halogen-free flame retardants is in cyanurate, cyanurate derivative, melamine polyphosphate, guanidinesalt and dicyandiamide salt It is at least one;
The fire retarding synergist is at least one of iron chloride, zinc borate, magnesia and aluminium oxide.
2. environmental protection flame retardant carbon fiber reinforced polyamide composite material according to claim 1, it is characterised in that:Described is poly- The mass fraction of acid amides is 40~50%;The mass fraction of the carbon fiber is 30~40%;The Kynoar Mass fraction is 12~20%.
3. environmental protection flame retardant carbon fiber reinforced polyamide composite material according to claim 1, it is characterised in that:
The polyamide is at least one of polyamide 6 and polyamide 66;
The dispersant is at least one of pentaerythritol esters dispersant, silicone dispersant and dendrimer;
Other described auxiliary agents are at least one of processing stabilizers and antioxidant.
4. environmental protection flame retardant carbon fiber reinforced polyamide composite material according to claim 1, it is characterised in that:Described answers It is 5 to close the mass ratio of halogen-free flame retardants and synergistic flame retardant in fire retardant:1~2:1.
5. environmental protection flame retardant carbon fiber reinforced polyamide composite material according to claim 3, it is characterised in that:Described is anti- Oxygen agent is phosphite ester kind antioxidant.
A kind of 6. preparation according to Claims 1 to 5 any one of them environmental protection flame retardant carbon fiber reinforced polyamide composite material Method, it is characterised in that including operating procedure in detail below:
(1) polyamide, Kynoar, composite flame-retardant agent, dispersant and other auxiliary agents are added in homogenizer and mixed It is even;
(2) mixed material in step (1) is added in double screw extruder by main spout, carbon fiber is through twin-screw extrusion Machine exhaust outlet is added in double screw extruder, and melt blending, extruding pelletization, that is, obtain environmental protection flame retardant carbon fiber reinforced polyamide and answer Condensation material.
7. the preparation method of environmental protection flame retardant carbon fiber reinforced polyamide composite material according to claim 6, its feature exist In:
The condition mixed described in step (1) is that mixing temperature is room temperature~80 DEG C, is stirred under the speed of 200~400r/min 10~30min;
The screw speed of the host of double screw extruder described in step (2) is 350~430r/min, hopper feed screw rod Rotating speed is 24~35r/min;
The temperature of melt blending described in step (2) is that the temperature of each bringing-up section of extruder is 180~255 DEG C.
8. according to Claims 1 to 5 any one of them environmental protection flame retardant carbon fiber reinforced polyamide composite material electronic apparatus, Application in high iron and field of power tools.
CN201510571583.8A 2015-09-08 2015-09-08 Environmental protection flame retardant carbon fiber reinforced polyamide composite material and its preparation method and application Active CN105111729B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510571583.8A CN105111729B (en) 2015-09-08 2015-09-08 Environmental protection flame retardant carbon fiber reinforced polyamide composite material and its preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510571583.8A CN105111729B (en) 2015-09-08 2015-09-08 Environmental protection flame retardant carbon fiber reinforced polyamide composite material and its preparation method and application

Publications (2)

Publication Number Publication Date
CN105111729A CN105111729A (en) 2015-12-02
CN105111729B true CN105111729B (en) 2018-04-17

Family

ID=54659856

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510571583.8A Active CN105111729B (en) 2015-09-08 2015-09-08 Environmental protection flame retardant carbon fiber reinforced polyamide composite material and its preparation method and application

Country Status (1)

Country Link
CN (1) CN105111729B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108993775B (en) * 2018-08-14 2020-05-08 锦洋高新材料股份有限公司 Preparation process of fluorite concentrate

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU7032201A (en) * 2000-06-15 2001-12-24 Saint Gobain Performance Plast Composite membrane for control of interior environments
US7939764B2 (en) * 2007-09-25 2011-05-10 Samuel Gottfried Fire, heat and high voltage cable protection wrap
CN101343409B (en) * 2008-08-27 2011-01-05 毛惠敏 Carbon fiber reinforced composite and preparation thereof
WO2013080820A1 (en) * 2011-11-29 2013-06-06 東レ株式会社 Carbon fiber-reinforced thermoplastic resin composition, and pellets and molded article thereof
CN104177821B (en) * 2013-05-27 2017-09-08 杜邦公司 Fire-resistant polyamide composite with improved impact resistance
CN104788860B (en) * 2015-04-20 2017-05-10 镇江铁科橡塑制品有限公司 Composite material for bearing wear plate and center plate wear plate of wagon and preparation method

Also Published As

Publication number Publication date
CN105111729A (en) 2015-12-02

Similar Documents

Publication Publication Date Title
CN104893088B (en) Ultraviolet light crosslinking low-smoke zero-halogen flame-retardant cable material and preparation method thereof
CN101225220B (en) Flame-retardant reinforced polybutylene terephthalate compound and production method thereof
CN104231575B (en) Halogen-free and phosphorus-free PBT enhanced composite material and preparation method thereof
CN104530694A (en) Regenerated PA6 (polyamide 6)-base flame-retardant electric-insulating heat-conducting composite material, and preparation method and application thereof
CN101280097A (en) Nanometer flame-proof polyethylene glycol terephthalate engineering plastics and preparation thereof
CN104559150A (en) Antistatic caprolactam heat-conducting material and preparation method thereof
CN104017363A (en) High-temperature-resistance flame-retardant glass fiber reinforced PA46/PA66 composite material and preparation method thereof
CN103059346A (en) Composite flame retardant, preparation method and application thereof
CN103333469A (en) Halogen-free flame-retardant PET (polyethylene terephthalate) composite material and preparation method thereof
CN103073881A (en) Nylon composition, preparation method and applications thereof
CN108102359A (en) A kind of environmentally protective, high-performance, high CTI flame-retardant reinforced nylon materials and preparation method thereof
CN106380838A (en) Flame retardant polyamide-based heat conduction material and preparation method thereof and application thereof in preparing plastic for LED head dissipation
CN107216650A (en) A kind of long glass fiber reinforced halogen-free reinforced nylon compound and preparation method thereof
CN103739928A (en) High-performance low smoke zero halogen power cable sheath material adopting silicon resin to enhance efficiency and preparation method thereof
CN103421294A (en) Halogen-free flame-retardant enhanced PC/ABS alloy and preparation method thereof
CN105111729B (en) Environmental protection flame retardant carbon fiber reinforced polyamide composite material and its preparation method and application
CN103739927B (en) Temperature resistant grade is low-smoke zero-halogen cable material formula and the preparation method of 150 DEG C
CN103849144A (en) Polyphenylene sulfide/nylon alloy material and preparation method thereof
CN105524301B (en) A kind of preparation method of microencapsulation basic zirconium phosphate and the halogen-free flame retardant PC being made from it
WO2012088743A1 (en) Flame retardant modified polypropylene composite improved by ceramic fibre and preparation process thereof
CN102108178A (en) Flame-retarding reinforced acrylonitrile-butadiene-styrene (ABS) composite containing ceramic fibers and preparation method thereof
CN107513213A (en) A kind of electrician's panel PP composite material and preparation method thereof
CN107474510B (en) High fluidity high rigidity halogen-free flame retardant PC/ABS mixture and preparation method thereof
CN108624027A (en) A kind of catalysis carbon-forming efficient halogen-free anti-inflaming PC/ABS mixtures and preparation method thereof
CN104693701A (en) Low-warpage halogen-free flame-retardant glass fiber reinforced PBT/AS alloy and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
C06 Publication
SE01 Entry into force of request for substantive examination
C10 Entry into substantive examination
CB02 Change of applicant information

Address after: Conghua City Ao town Guangzhou city Guangdong province 510940 Longtan Jubao Industrial Zone

Applicant after: GUANGZHOU SUPER-DRAGON ENGINEERING PLASTICS CO., LTD.

Address before: Conghua City Ao town Guangzhou city Guangdong province 510945 Longtan Jubao Industrial Zone

Applicant before: Guangzhou Super-Dragon Engineering plastic Co., Ltd.

COR Change of bibliographic data
GR01 Patent grant
GR01 Patent grant
PE01 Entry into force of the registration of the contract for pledge of patent right

Denomination of invention: Environment-friendly flame-retardant carbon fiber reinforced polyamide composite and preparation method and application thereof

Effective date of registration: 20190530

Granted publication date: 20180417

Pledgee: Conghua Branch of Guangzhou Bank Co., Ltd.

Pledgor: GUANGZHOU SUPER-DRAGON ENGINEERING PLASTICS CO., LTD.

Registration number: 2019440000196

Denomination of invention: Environment-friendly flame-retardant carbon fiber reinforced polyamide composite and preparation method and application thereof

Effective date of registration: 20190530

Granted publication date: 20180417

Pledgee: Conghua Branch of Guangzhou Bank Co., Ltd.

Pledgor: GUANGZHOU SUPER-DRAGON ENGINEERING PLASTICS CO., LTD.

Registration number: 2019440000196

PE01 Entry into force of the registration of the contract for pledge of patent right
PC01 Cancellation of the registration of the contract for pledge of patent right

Date of cancellation: 20200821

Granted publication date: 20180417

Pledgee: Conghua Branch of Guangzhou Bank Co.,Ltd.

Pledgor: GUANGZHOU SUPER-DRAGON ENGINEERING PLASTICS Co.,Ltd.

Registration number: 2019440000196

PC01 Cancellation of the registration of the contract for pledge of patent right